In this article, experiment and theory are combined to analyze Pb and Cu underpotential deposition (UPD) on similar to 1.7 nm Au nanoparticles (NPs) and the AuPt structures that result after galvanic exchange (GE) of the UPD layer for Pt. Experimental Pb (0.49 ML) and Pt (0.50 ML) coverages are close to values predicted by density functional theory-molecular dynamics (DFT-MD, 0.59 ML). DFT-MD reveals that the AuNPs spontaneously reconstruct from cuboctahedral to a (111)-like structure prior to UPD. In the case of Pb, this results in the random electrodeposition of Pb onto the Au surface. This mechanism is a consequence of opposing trends in Pb-Pb and Pb-Au coordination numbers as a function of Pb coverage. Cu UPD is more complex, and agreement between theory and experiment takes into account ligand effects (e.g., SO42- present as the electrolyte) and the electric double layer. Importantly, AuPt structures formed upon Pt GE are found to differ markedly depending on the UPD metal. Specifically, cyclic voltammetry indicates that the Pt coverage is similar to 0.20 ML greater for Cu UPD/Pt GE (0.70 ML) than for Pb UPD/Pt GE (0.50 ML). This difference is corroborated by DFT-MD theoretical predictions. Finally, DFT-MD calculations predict the formation of surface alloy and core@shell structures for Pb UPD/Pt GE and Cu UPD/Pt GE, respectively.